INTRODUCTION TO TREATMENT OF TANNERY EFFLUENTS

What every tanner should know about effluent treatment

Introduction to treatment of tannery effluents
What every tanner should know about effluent treatment

UNITED NATIONS INDUSTRIAL DEVELOPMENT ORGANIZATION Vienna, 2011

Copyright © 2011 by the United Nations Industrial Development Organization.
The designations employed and the presentation of material in this publication do not imply the expression of any opinion whatsoever on the part of the European Union (EU) or the Secretariat of the United Nations Industrial Development Organization (UNIDO) concerning the legal status of any country, territory, city or area, or of its authorities, or concerning the delimitation of its frontiers or boundaries. Designations such as “industrialized,” “developed” or “developing” countries are used for statistical convenience and do not necessarily express a judgment about the stage reached by a particular country or area in the development process. Mention of firm names or commercial products does not imply endorsement by EU, UNIDO or the other project partners. Materials in this publication may be freely quoted or reprinted, but acknowledgement is required, and UNIDO must receive a copy of the publication containing the quotation or reprint. Reduction of environmental threats and increase of exportability of Bangladeshi leather products (Re-Tie Bangladesh) is a project co-funded by the European Commission under the SWITCH Asia Programme and implemented by the project partners: SEQUA (lead partner), bfz, BFLLFEA, BTA, DCCI and UNIDO.

The paper Introduction to treatment of tannery effluents was prepared based on technical inputs by J. Buljan and I. Kral. Valuable contributions by G. Clonfero, M. Bosniç and F. Schmel are gratefully acknowledged.

8.1 Submersible pump 1.8. costs. management 7.4 Fine screening 1.3 Pumping/lifting 1.3.1 Objectives 1. Monitoring.2 Belt-filter press 1. oxidation ditch 2.3 Centrifuge 1.1 Objective and basic principles 2. Biological (secondary) treatment 2.2 Main operational parameters 2.1 Mechanical sludge dewatering 4. flocculation) 1.8.2. Advanced (tertiary) treatment 4.2 Screw (Archimedes) pump 1.2. Conclusions 6 12 12 12 12 13 14 14 15 15 16 17 18 21 22 23 25 26 27 29 29 30 31 32 34 36 37 37 37 37 38 39 42 46 .8. Sludge handling 4.1 Bar screening.3.6 Secondary sedimentators 2. OSH.Introduction to treatment of tannery effluents 3 Contents Foreword: Why this booklet? 1.7 Settling – primary sedimentation 1.3 Self-cleaning screens 1.4 Sludge-drying beds 2. The issue of bad odour 6.1 Sludge thickener 1.2. removal of larger solids 1.2 Removal of grit and floating matter 1.8 Sludge dewatering 1.7 Anaerobic biological treatment 3.5 Aeration basins.4 Aeration devices 2.6 Chemical treatment (coagulation.3 Other operational parameters 2.2 Utilization and disposal 5.2 Screening 1.5 Equalization – homogenization – sulphide oxidation 1. Primary treatment 1.

Schematic view of the coagulation and flocculation system 17. 2. Submersible pump 11. Schematic views of sludge-drying beds 27. Cross section of floating aerator 31. Archimedes lifting pump 12. outer flow 13. Cross section of a sludge dewatering centrifuge 26. Parkwood type 9. Rough bar screen. An example of mass balance in leather processing An example of average total pollution load An example of pollution load. Self-cleaning screen. submersed turbine aerator 32. Flowchart of in-house segregation of streams 5. Simple. side view 6. 6. Cross section of a belt-type press for sludge dewatering 25. Rotary-drum (Konica) screen. Cross section of a progressing cavity pump for sludge transfer 22. Overview of the tanning industry 2. Rotary-drum fine screen. Schematic view of a dissolved-air flotation (DAF) unit 21. 3. inner flow 14. Schematic view of an equalization. Sources and types of pollutants generated in leather processing 3. non-aerated grit-and-floating-matter removal chamber 8. 5. Some simple laboratory utensils 18. Forced-air. hydrosieve type 10.4 Contents Tables Table Table Table Table Table Table Table 1. Rough bar screen. Cross section of a gravity thickener 23. Cross section of a typical circular sedimentation tank 19. Simplified flowchart of the biological (secondary) tannery effluent treatment 6 8 10 10 12 13 13 14 14 15 15 16 16 17 18 19 20 21 21 22 23 23 24 25 26 27 28 30 32 33 33 35 40 . Schematic diagram of oxidation ditches 33. Surface (floating) aerators 30. operation principle 7. homogenization tank 15. Layout of in-house segregation of streams 4. Simplified flowchart of the physical-chemical (primary) tannery effluent treatment 28. conventional process Purification efficiency of treatment stages referred to raw effluent Characteristics of sludge dewatering equipment Dry matter content in sludge Poisoning effects of hydrogen sulphide gas (H2S) 7 7 9 27 37 38 44 Figures Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure 1. Cross section of a recessed-plate press for sludge dewatering 24. Cross section of a rectangular sedimentation tank 20. Self-cleaning. 4. 7. Venturi-type ejector often installed for mixing and aeration in the homogenization tank 16. A simplified flow diagram of the activated sludge process 29. rotary-brush screen.

Italy and India 18. Recessed-plate filter press with container for dewatered sludge 6. Sedimentation tank in operation 5. diagram. Bottom air diffuser grid with one section and fine-bubble dome diffuser 10. A dialogue between a tanner and an environmental engineer 16. "Flocs" after coagulation. Sludge dewatering centrifuge (the lid is up for better view) 8. Fine-bubble difusers. General view of inputs and outputs in the leather sector 2. Classification of mechanical aerators 9. Typical tannery ETP auxiliary chemicals and their dosing 19. Structure of average treatment costs at selected CETPs in India in 2005 Figure 36. Oxidation ditch in operation 13. Basic plant monitoring and control 17. Schematic chart of typical effluent treatment setup for clusterss in developing countries Figure 38.Introduction to treatment of tannery effluents 5 Figure 34. dome and tubular type 11. A model of rotary screening drum 5. flocculation 3. Types of sedimentation tanks 6. Schematic view of constructed wetland – reed beds 13. Schematic chart of typical effluent treatment setup in industrialized countries Figure 39. Submersed turbine aerators in oxidation ditch 12. Discharge limits for treated tannery effluents in France. An example of CETP management setup 41 42 42 43 43 45 Photographs Photo Photo Photo Photo Photo Photo Photo Photo Photo Photo Photo Photo Photo 1. Reverse osmosis (RO): principle. Belt press with transporter for dewatered sludge 7. Distribution of average total costs at selected CETPs in Italy Figure 37. Simplified flowchart of a full-fledged tannery effluent treatment plant Figure 35. Classification of pumps 4. Chrome-recovery unit using NaOH 3. Aerated static composting pile 14. Typical fluxogram of an ETP 15. Personal hydrogen-gas monitor 11. Sedimentation tank (empty) 4. Photos and cross section of a circular sedimentation tank 7. Environmental effects of the main constituents of tannery effluents 20. References 48 48 49 50 50 51 51 52 53 53 54 55 56 57 58 59 60 61 62 67 . Sludge production in leather processing 8. Containers for solid waste 20 20 22 22 24 25 26 33 34 34 35 36 38 Annexes Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex Annex 1. Scheme of the membrane bioreactor (MBR) 10. Coagulant/flocculant dosing station 2. photo of a small RO unit 12. Surface aerators 9.

Yet. Overview of the tanning industry The purpose of this booklet is to help tanners and tannery managers get acquainted with basic principles and methods of tannery effluent treatment.. ammonia nitrogen by 80%. Obviously. therefore. it is possible to decrease significantly the pollution load. In order to keep it short and concise. By applying industrially proven low-waste advanced methods such as the use of salt-free preserved raw hides and skins. environmental authorities and NGOs. there is the widespread misperception that vegetable tanning is environmentally harmless (in reality its effluents have very high. this publication focuses on combined chrome tanning. remains the supreme priority. and chromium by up to 90%. advanced chrome management systems. etc. Figure 1.6 Why this booklet? Foreword: Why this booklet? Confronted with increasing legal and social pressures. for an in-depth understanding of the complexities of dealing with effluents and solid wastes (sludge). low-ammonia or ammonia-free deliming and bating. total (Kjeldahl) nitrogen by 50%. . there are many simplifications and omissions of details. pollution prevention. This knowledge should make them better equipped for a dialogue with the factory's own environmental unit. no tanner can afford the luxury of not being familiar with the main issues and principles of environmental protection pertaining to tannery operations. the persistent promotion of cleaner leather processing. difficult to treat COD). namely: COD and BOD5 by more than 30%. Finally. which ultimately leads to lower treatment costs. there is still a considerable amount of pollution load to be dealt with by end-of-pipe methods. sulphides by 80-90%. it is recommended to consult the extensive literature on this subject. chlorides by 70%. sulphates by 65%. hair-save liming. despite all preventive measures. which is by far the most prevailing leather tanning method.

The tables below and the chart on overleaf may give a general idea. water consumption: 45 m3/tonne . The spread of cleaner technologies and processes has been neither spontaneous nor extensive. An example of average total pollution load – concentration in combined raw effluent.. and reduced content of specific pollutants such as heavy metals and electrolytes. improved uptake of chemicals. process. tanners are not quick in adopting them. the usual reference being one tonne of wet-salted hides. Pollution load Due to variations in raw material. it is small wonder that figures about pollution load in the literature vary a lot and should be interpreted very cautiously. For all the claims about favourable cost-benefit ratios and/or environmental benefits to be derived from many of these technologies. be it due to inertia. An example of mass balance in leather processing Table 2.Introduction to treatment of tannery effluents 7 Cleaner technologies The pressure to adopt cleaner technologies normally emanates from environmental imperatives such as the need to meet specific discharge norms. conventional process. higher costs or the limitations mentioned earlier. chemicals. water consumption. The typical primary targets are: lower water consumption. Table 1. better quality/re-usability of solid waste. reduce treatment costs or comply with occupational safety and health standards. etc.

8 Why this booklet? Figure 2. Sources and types of pollutants generated in leather processing .

acidic. The goal is to reduce or remove organic matter. While generally lower water consumption is very desirable (nowadays in well managed tanneries. the obvious is often overlooked: the same amount of pollutants at lower water consumption means lower hydraulic load (volume) but higher concentration – not always easy to treat. solids. suspended solids (SS). mainly from post-tanning operations (fat-liquoring. Wastewater treatment is a multi-stage process to purify wastewater before it enters a body of natural water. there are no two identical ETPs. nutrients. thus. • Soaking and other general effluents. An example of pollution load. • Somewhat paradoxically. Therefore. water from fleshing and splitting machines. are: • Effluents emanating from the beam-house – liming.Introduction to treatment of tannery effluents 9 To avoid possible confusion arising due to differences in water consumption. Cr and other pollutants since each receiving body of water can only receive certain amounts of pollutants without suffering degradation. total dissolved solids (TDS) and others. • It is important for a tanner to understand the relation between the leather technologies applied and wastewater treatment in order to reduce the overall cost of treatment. or it is applied to the land. Table 3. Cr. it is below 30 m3/tonne). The three main categories of tannery wastewater. dyeing) – low Cr content. their pH is high. COD. deliming/bating. sammying) – high Cr content. it obviously results in considerably higher concentrations of pollutants. but they are chrome-free. • Effluents emanating from the tanyard (tanning and re-tanning. it is important to bear in mind the following: • The design of an effluent treatment plant (ETP) is always tailored to the requirements of a specific site. they contain sulphides. it is practical to indicate the amount of pollutants generated per tonne of raw-hide input. each one having very distinctive characteristics. . each effluent treatment plant must adhere to discharge standards – limits usually promulgated by the relevant environmental authority as allowable levels of pollutants. or it is reused. for practical reasons expressed as BOD5. • Pollutants contained in effluent cannot disappear. they are only converted into something which is environmentally more acceptable or easier to dispose of (sludge). conventional process Treatment Before turning to treatment itself.

10 Why this booklet? Figure 3. treatment of liming effluents and pre-treatment of mixed effluent . Flowchart of in-house segregation of streams. Layout of in-house segregation of streams. including chrome recycling and oxidation of sulphides in liming effluent Figure 4. including chrome recycling.

Introduction to treatment of tannery effluents 11 It is very important to segregate these streams and to pre-treat them separately according to their characteristics to avoid possible safety risks (formation of deadly hydrogen sulphide) and to reduce the cost of treatment and sludge disposal (to avoid contamination of sludge with Cr). and H2O). The volume and pollution load of sanitary wastewater in comparison with industrial wastewater is insignificant. is still by far the most frequent killer in tannery accidents. Approximately 25-50% of the incoming biochemical oxygen demand (BOD5). Biological treatment (secondary) In most cases. and the removal of materials that will float (scum) by skimming. Several aerobic biological processes are used for secondary treatment and the differences among them have to do primarily with the manner in which oxygen is supplied to the micro-organisms and with the rate at which organisms metabolize the organic matter. in the case of common effluent treatment plants (CETPs) servicing tannery clusters often found in developing countries. Physical-chemical treatment (primary) The objective here is the removal of settleable organic and inorganic solids by sedimentation. but also to significantly reduce the content of chrome and sulphides before the effluent is discharged into the collection network. secondary treatment follows primary treatment. The effluent and sludge from primary sedimentation are referred to as primary effluent and sludge. The mixing of liming and tanning streams gives rise not only to the obnoxious smell typical of poorly managed tanneries. Very arbitrarily and not quite consistently we speak of the following main phases of treatment: Preliminary treatment Typically. Furthermore. “cleaned” effluent and sludge because inherently the primary aim of wastewater treatment is the removal of solids and some potentially hazardous substances from the wastewater. Their role is to remove large particles. Advanced (tertiary) treatment Tertiary or advanced wastewater treatment is employed to reduce residual COD load and/or when specific wastewater constituents are not removed by previous treatment stages. its goal being the removal of biodegradable dissolved and colloidal organic matter using aerobic biological treatment processes. and 65% of the oil and grease are removed during primary treatment. and the latter are removed from the wastewater. thereby producing more micro-organisms and inorganic end products (principally CO2. it is essential to have pre-treatment units installed in individual tanneries. sand/grit and grease. which occur mainly in inadequately ventilated spaces. hydrogen sulphide (H 2S). Aerobic biological treatment is carried out in the presence of oxygen by aerobic micro-organisms (principally bacteria) that metabolize the organic matter in the wastewater. 50-70% of total suspended solids (SS). Sludge handling and disposal Effluent treatment plants produce treated. biologically degradable organic substances are converted into bacterial cells. NH3. the resulting lethally poisonous gas. especially in pits and channels. .

pipes and possibly sewer lines. flocculation) Settling Sludge dewatering2 1. remove almost completely Cr and sulphides. and considerably reduce the BOD and COD content. • To significantly decrease the BOD/COD load and thus simplify the biological treatment phase and reduce its cost. • To adjust pH and eliminate toxic substances (sulphides) and avoid shock loads that can negatively affect the rather sensitive biological treatment. 2 Primary and secondary sludge are handled/dewatered together. usually before fine screening and pumping. • To mix and balance well different tannery streams and thus produce homogenized “raw material” that can be treated in a consistent manner. side view 1Quite often a grease-and-sand trap is also included. Rough bar screen. Basic steps: Screening (bar. the purpose is to eliminate the coarse matter. To summarize. since some ETPs have only primary treatment and the main part of sludge is generated during that stage.2.12 Primary treatment 1. .1 Bar screening.1 Objectives • To eliminate the coarse material normally present in the raw wastewater that could clog/block pumps. however. Primary treatment 1. remove the major part of suspended solids. removal of larger solids Figure 5. sludge dewatering is covered here.2 Screening 1. self-cleaning)1 Pumping/lifting Fine screening Equalization and sulphide oxidation Chemical treatment (coagulation.

Simple.2 Removal of grit and floating matter A simple.2. Figure 6. . non-aerated grit-and-floating-matter removal chamber is usually placed in a horizontal gravity channel immediately after the rough screen. aerated systems for the removal of grit and floating matter.Introduction to treatment of tannery effluents 13 1. non-aerated grit-and-floating-matter removal chamber Large ETPs require more sophisticated. operation principle Figure 7. Rough bar screen.

For medium-scale ETPs. Depending on specific requirements (capacity/flow). hydrosieve type 1. Self-cleaning.3 Self-cleaning screens Figure 8. at least one. Parkwood type Figure 9. different types of pumps are used. often more pumping/lifting stations are needed.3 Pumping/lifting It is not possible to transfer effluents throughout the ETP by gravity only. submersible pumps are generally used for this purpose. the first typically located before the rotary screen.14 Primary treatment 1. . rotary-brush screen.2. screw (Archimedes) pumps are preferred. Self-cleaning screen. for large-volume ones.

Schematic view of an Archimedes-type lifting pump .Introduction to treatment of tannery effluents 15 The scheme of submersible pump positioning (usually with a stand-by pump) is shown below: 1.1 Submersible pump Figure 10.2 Screw (Archimedes) pump Figure 11.3.3. Submersible pump 1.

Fine screening Fine screening should drastically reduce the amount of fine suspended solids. inner flow . The figures below show rotary-drum screens with outer and inner flow.4. Rotary-drum (Konica) screen.16 Primary treatment 1. Rotary-drum fine screen. outer flow Figure 13. Figure 12.

The inlet and the outlet of the equalization tank should be as far away from each other as possible to allow proper mixing (and no short-circuiting). attention is focused on the energy required to keep the solids in suspension (some 50 W/m3).Introduction to treatment of tannery effluents 17 1. is about 20 g per cubic meter of tank capacity. Whichever the mixing/aeration system chosen. Schematic view of an equalization. homogenization tank Approximately 1 kg of O2 is needed to oxidize 1 kg of S2. it is necessary to be possible to remove the mixing device without stopping the treatment process. This is achieved by using mixing-cum-aeration devices such as diffused-air systems (preferred). industrial purity. Figure 14. whereas the oxygen transfer efficiency is about 1. in practice. to avoid settling of solids. the volume of the equalization tank corresponds to the total daily effluent discharge.= 1 kg O2 = 1kWh). which is then sufficient for sulphide oxidation. Again. and fixed or floating aerators (lately avoided due to lower efficiency and the problem of aerosols). MnSO4 · 4 H2O.e. the amount of catalyst. In practice.5 Equalization – homogenization – sulphide oxidation The main aims here are: • homogenization of the effluent (quantity and quality).to thiosulphate. i. . It is very important to keep all particulate matters in suspension. to play it safe.. and • sulphide elimination. Venturi ejectors.5 kg O2/kWh (simplified approximation: 1 kg S2. mostly by catalytic oxidation.

Venturi-type ejector often installed for mixing and aeration in the homogenization tank A typical equalization tank will have transfer pumps for equalized effluent. they are two distinct processes usually carried out in sequence as a combination of physical and chemical procedures.18 Primary treatment Figure 15. sometimes “flocculation” is understood as the second stage of “coagulation”. causing them to repel each other. Cationic coagulants provide positive electric charges to reduce the negative charge (zeta potential) of the colloids. transfer time and head. In wastewater treatment operations. In fact. Since this prevents these charged particles from colliding to form larger masses. The pumping line(s) are also a good place to set an electro-magnetic flow meter. especially of fine and colloidal matter. 1. . Finely dispersed solids (colloids) suspended in wastewater are stabilized by negative electric charges on their surfaces. the processes of coagulation and flocculation are employed to separate suspended solids from water. the particles collide to form larger particles (flocs). they do not settle. Care must be taken not to overdose the coagulants as this can cause a complete charge reversal and thus re-stabilize the colloid complex. Coagulation is the destabilization of colloids by neutralizing the forces that keep them apart. Rapid mixing is required to disperse the coagulant throughout the liquid. The capacity of the pumps is based on tank capacity.6 Chemical treatment (coagulation. flocculation) Chemicals are added in order to improve and accelerate the settling of suspended solids. or the single term – be it “coagulation” or “flocculation” – is used to describe both. As a result. called flocs. One pump of cast iron with inside parts of stainless steel and one stand-by pump are sufficient unless effluent volume is very high (say 1.500 m3/d or more). These terms are often used interchangeably.

The most frequently used coagulants in tannery effluent treatment are: . Schematic view of the coagulation and flocculation system .iron sulphate: industrial FeSO4 · 7H2O . The newly formed agglomerated particles are quite fragile and can be broken apart by shear forces during mixing. Once suspended particles are flocculated into larger particles. In this process it is essential that the flocculating agent be added by slow and gentle mixing to allow for contact between the small flocs and to agglomerate them into larger particles. they can usually be removed from the liquid by sedimentation. The inorganic coagulants are compounds that break colloidal suspensions and help floc forming. Figure 16. straining or floatation.Introduction to treatment of tannery effluents 19 Flocculation is the action of polymers to form bridges between flocs and bind particles into large agglomerates or clumps.iron chloride: industrial FeCl3 · 6H2O . The flocculation reaction not only increases the size of floc particles in order to settle them faster. but also affects the physical nature of flocs making them less gelatinous and thereby easier to dewater. filtration.lime: industrial calcium hydroxide Ca(OH)2 Coagulant aid – flocculants – are water-soluble organic (anionic) polyelectrolytes that support agglomeration of colloidal and very fine suspended matter thus enhancing the impact of coagulation. Care must also be taken not to overdose the polymer as doing so will cause settling/clarification problems.alum: industrial aluminium sulphate Al2(SO4)3 · 18H2O .

Figure 17. The contact time in the flash mixer is about 5 minutes for coagulation and some 20 minutes for flocculation. in the latter case. slow mixing to avoid floc shearing is essential.20 Primary treatment For optimal results. the other for feeding the solution to the effluent. Hence. these chemicals also influence not only pH (acidification) but also TDS. Coagulant/flocculant dosing station Photo 2. “Flocs” after coagulation-flocculation . Some simple laboratory utensils Chemicals (pre)dissolved in small tanks with stirrers are usually added in the flash mixers – special “boxes” for rapid mixing placed before the primary settling tank. The feeding of chemicals is done by dosing pumps. On-the-spot investigation – jar tests using either sophisticated apparatus or simple tools (shown below) – is a must. levels of chemical dosing can be better controlled. the usable volume of the coagulation and flocculation tank respectively should be 60 · 1/12 = 5 m3 and 60 · 1/3 = 20 m3. if the capacity of the equalized effluent transfer pump is 60 m3/h. for example. in addition to costs. Ideally. Photo 1. two tanks should be available for the preparation of each chemical – one for solution preparation. it should not be overlooked that. appropriate dosing is essential. By having two tanks.

day). • surface hydraulic loading. due to the quantity (4-6 g/l) and flocculent nature of tannery effluent solids. typically 1 to 2 m3/m2 per hour. etc. A mechanical device (scraper) is necessary in larger settling tanks.7 Settling – primary sedimentation The main objective at this stage is the removal of suspended solids. waxes. expressed in m3/m2 of tank surface per hour or m/h. The key design parameters are: • detention time – usually 1 to 2 hours (vertical clarifiers of the Dortmund type). it is useful in controlling the primary sedimentation as well. Cross section of a typical circular sedimentation tank Figure 19. Cross section of a rectangular sedimentation tank with travelling bridge shown in two positions . Circular tanks are generally preferred as recirculation is easier. are also separated here. mineral oils. (“grease”). expressed in kg/m2 and indicating the quantity of SS crossing the surface area of the tank over a certain time span (hour. The surface solids rate is most frequently used in the design of sludge thickeners but. floating non-fatty materials. various constituents such as fats. not already removed in the grit-andoil chamber (usually positioned between screening and equalization). however. Primary settling tanks (clarifiers) are either circular (more commonly used) or rectangular with continuous grease (scum) removal at the top and sludge removal at the bottom.Introduction to treatment of tannery effluents 21 1. • surface solids rate. Figure 18.

.22 Primary treatment Photo 3. Schematic view of a dissolved-air flotation (DAF) unit 1. Sedimentation tank (empty) Photo 4. solids are removed by flotation.8 Sludge dewatering The sludge drawn from the bottom of the tank is in the form of slurry with a dry-solid (DS) content of only 2-4%. usually by the dissolved-air flotation (DAF) system. Sedimentation tank in operation In some cases. special pumps – usually of the Mohno type – are used. mainly due to space shortage. For its evacuation. Figure 20.

1. This is usually achieved by: (i) thickening in sludge thickeners (very much like circular clarifiers).8. Cross section of a gravity thickener . it is necessary to reduce drastically the water content. the key parameter for equipment selection is the achievable dry matter content in the dewatered sludge.Introduction to treatment of tannery effluents 23 Figure 21. In addition to power and chemical requirements. Cross section of a progressing cavity pump for sludge transfer For further handling and disposal of sludge. (ii) mechanical dewatering in filter presses.1 Sludge thickener The construction of the sludge thickener is in practice identical with that of the sedimentator although in some cases the Dortmund type with self-desludging slopes is also used. (iii) natural drying in sludge-drying beds. Figure 22. belt-filter presses or decanters (centrifuges).

Cross section of a recessed-plate press for sludge dewatering Photo 5.24 Primary treatment Figure 23. Recessed-plate filter press with container for dewatered sludge .

Cross section of a belt-type press for sludge dewatering Photo 6. Belt press with transporter for dewatered sludge .2 Belt-filter press Figure 24.Introduction to treatment of tannery effluents 25 1.8.

8. depending on initial concentration. Cross section of a sludge dewatering centrifuge Photo 7. Sludge dewatering centrifuge (the lid is up for a better view) Mechanical dewatering effects are nowadays from 30 to 40% DS. improving wear and tear resistance (especially in the case of sludge containing fine sand) as well as by lowering irritating noise. Figure 25. centrifuges have succeeded in conquering a lot of ground in the treatment of tannery effluents.26 Primary treatment 1.3 Centrifuge By increasing dewatering level. chemical preconditioning and equipment make. .

its chrome content depends on the type and efficiency of the chrome management system applied. and (ii) dewatered sludge – with approximately 40% DS. For these reasons. Schematic views of sludge-drying beds The products of primary treatment are: (i) primary treated effluent – overflow from the primary settling tank – with only residual amounts of chrome and sulphide and significantly reduced BOD. there is the problem of malodour.4 Sludge-drying beds Easily constructed with locally available materials. they are not easy to clean and made ready for the next batch. drying beds were perceived as the best solution for tanneries in hot-climate developing countries.30 kg BOD5/kg MLSS. Figure 26. Purification efficiency of treatment stages referred to raw effluent . Usually. For the fortunate tanneries coupled to the sewage system. sludge-drying beds are still used mainly by small tanneries not close to residential areas and/or as fall-back units used during breakdowns of mechanical dewatering equipment.8. the output during rainy seasons drops considerably. However. COD and SS content.Introduction to treatment of tannery effluents 27 1. they require a lot of area. etc. on-site treatment ends here – the biological treatment takes place together with urban wastewater in large WWWs. * Approximately at the load level of 0.0 kg O2/kg BOD5 and MLSS 3300 g/m3 Table 4. oxygen requirement of 2. industrial effluents are only a small fraction of the total volume so that the salinity (TDS) they bring along does not represent a problem.

Simplified flowchart of the physical-chemical (primary) tannery effluent treatment .28 Primary treatment Figure 27.

biological process. The microbial community that does that job comprises various species of bacteria. While biological treatment may be aerobic. exceptionally. the composition of the population depending on a plethora of factors. even nematodes. fungi. The qualitative biochemical reaction taking place in the organic matter stabilization process can be summarized in the following manner: Inert matter + organic matter + oxygen + nutrients + micro-organisms new micro-organisms + CO2 + H2O + additional inert matter Simply said. Biological (secondary) treatment 2. in countries with a hot climate and where a lot of land is available.. we stimulate micro-organisms to convert (eat and digest) harmful. facultative or anaerobic (or some combination thereof). stable compounds like water and carbon dioxide. at a highly accelerated pace. The remaining suspended and colloidal solids are removed by flocculation and adsorption. membrane bioreactors (MBRs) have not made significant inroads in the tanning sector. sometimes rotifers (multicellular animals only found in very stable activated sludge with long retention times). i. however. anaerobic treatment is used only in sludge digestion. the efficiency of this treatment largely depends on the biodegradability of the polluting substrate. in practice. lakes). primarily their sulphide/sulphate content. but under controlled conditions and. which uses the metabolism of microorganisms to remove substances causing oxygen demand. in practice. facultative (preferably aerated/facultative) lagoons are also used. almost only aerobic systems are used.Introduction to treatment of tannery effluents 29 2. The COD is always greater than its BOD. protozoa. The activated sludge process is an aerobic. the most widely used method is (complete-mix) activated sludge treatment with extended aeration. The biological treatment duplicates processes that take place in nature. COD is the quantity of oxygen consumed for the total oxidation of the oxidizable matter (organic and inorganic) with dichromate as the oxidizing agent. Among many variations of the aerobic process. its inherent capacity to decompose by biological processes. Due to the inherent characteristics of tannery effluents. usually over only five days instead of 20. despite some very interesting features.e. oxygen-demanding organic compounds into an environmentally more acceptable form (micro-organisms) and low-energy. 3 Let us recall that BOD is defined as the quantity of oxygen required during the stabilization of decomposable organic and oxidizable inorganic matter by aerobic biological action under standard conditions. The manometric method is even faster but less accurate and reliable. . especially.1 Objective and basic principles The main objective at this stage is to further reduce the amount of organic (expressed as BOD and COD)3 and other substances still present in the effluent after the primary treatment and thereby satisfy the standards/limits for discharge into surface waters (rivers.

A simplified flow diagram of the activated sludge process Generally. F: volume of treated effluent (m3/day) aeration tank volume (m3) total BOD5 applied (kg/day) F = (f x Q)/1. its day-to-day running requiring considerable skills and experience. 2. T: T = (V/Q) x 24 where V is aeration tank volume (m3) A uniform inlet flow over the entire day provides optimum conditions for absorbing the effect of possible peaks of organic load or toxic substances (shock loads) and enhancing the efficiency of secondary sedimentation. the biological stage is the most complex part of the overall effluent treatment process. M: M = (MLSS x V)/1000 where MLSS is the concentration of SS in mixed liquor in the aeration tank (mg/l) • Loading factor.2 Main operational parameters The main operational parameters – expressions important to understanding the process – are: • Total influent volume.30 Secondary treatment Figure 28. . V: • Organic loading. Q: • Tank volume. Due to the difficulty of obtaining reliable BOD5 values.000 where f is the BOD5 of the influent (mg/l) • Mixed liquor suspended solids. with highest investment and operational costs. F/M: BOD5 kg per day per kg of mixed liquor suspended solids (MLSS) in the aeration tank (mg/l) • Hydraulic retention time. COD is sometimes used. The BOD here is in practice taken to represent the amount of food provided to the micro-organisms contained in the system.

as the temperature is raised 10-30°C. Extended aeration plants are characterized by the introduction of wastewater directly into the reactor basin.15-0. The nutritional balance of an aerobic system is primarily based upon satisfying the requirements of the cell structure produced by the removal of BOD from waste. typical for tannery effluents. A BOD : N : P ratio of 100 : 5 : 1 in the waste usually insures adequate nutrition. In alkaline wastes. is usually longer than 24 hours. Extended aeration units are usually operated in such a way as to keep the DO of the mixed liquor at about 2 mg/l. it is about 80-100%. and the return activated sludge (RAS) – the volume of settled biological sludge recycled to the aeration tank as a percentage of the influent volume Q. low sludge wastage and high MLSS: the F/M (kg BOD/kg MLSS per day) ratio is only ≤ 0. regrettably. pH. it is one of the most important factors determining the efficiency/performance of wastewater biological treatment. in particular.0).5 with an effective process range of 6-9. The F/M. the growth rate increases. 2. higher temperature negatively affects the water solubility of oxygen and the oxygen transfer rate (solubility decreases with a rise in temperature). . The following parameters are.05 – 0.3 Other operational parameters Quite important are also parameters like the sludge age expressed as the mean cell-residence time (MCRT). Tannery effluent is very rich in nitrogen and sometimes poor in phosphorus.4) or high-load type (0. Generally. However. it cannot be determined quickly.0 and 7. the extended aeration process. the reaction with CO2 produced by respiration neutralizes the excess alkali. Nutrients. the food to biomass (floc) ratio is a parameter crucial for operational conditions and the performance of the biological process. high sludge return ratio. in the extended aeration process. Adjustment with lime or other alkali becomes necessary only if pH drops below 6.4-1. long aeration. regularly monitored: Dissolved oxygen (DO) is the content of molecular oxygen in the aeration tank (mg/l). an increase of the aeration rate becomes necessary during the hot season. generally not less that 20 days. on-the-spot. For this reason. Efficient and successful biological oxidation requires a minimal quantity of nitrogen and phosphorus. making addition of acid unnecessary.Introduction to treatment of tannery effluents 31 Hydraulic retention time is actually the average time (in hours) the influent spends passing through the aeration tank. Temperature affects the metabolic and growth rates of the organisms responsible for the biological processes. The optimum pH range for aerobic processes is between 7.1 in contrast to the conventional (0.

the key criterion is the amount of air (oxygen) transfer per kW installed. Surface aerators Radial flow.32 Secondary treatment Sludge volume index (SVI) is the volume occupied by 1 g of activated sludge after settling the aerated mixed liquor in a 1. Surface (floating) aerators . Well settleable and mineralized sludges have SVI <100. low speed. 20-60 rpm Axial flow. 2. reliability.. very helpful in controlling the activated sludge process.000 ml graduated cylinder or Imhoff cone for 30 minutes. Diffusers Bubblers – porous and non-porous diffusers Tubular Jets (developed from Venturi ejectors) Figure 29.4 Aeration devices Water (effluent) aeration is important business that employs a wide range of equipment. etc. Here is one – rather arbitrary – classification: a. 300-1200 rpm Brush rotor (oxidation ditch) b. high speed. In addition to cost. especially in determining return sludge pumping requirements to maintain different mixed-liquor concentrations. It provides a good indication of sludge compacting characteristics. Submerged turbines c.

Introduction to treatment of tannery effluents 33 Figure 30. submersed turbine aerator . Surface aerators Figure 31. Cross section of floating aerator Photo 8. Forced-air.

34 Secondary treatment Photo 9. with rotary-brush or vertical-rotor (carrousel) aerators that extend across the width of the ditch. . Fine-bubble difusers. oxidation ditch The possibly best biological treatment of tannery effluents is the oxidation ditch (OD) and its various derivatives – a circular aeration basin (racetrack-shaped). Bottom air diffuser grid with one section and fine-bubble dome diffuser Photo 10.5 Aeration basins. dome and tubular type 2.

nitrification and denitrification In addition to its simple construction and easy maintenance.Introduction to treatment of tannery effluents 35 Figure 32. It is even possible to combine several ovals and maintain different aeration regimes suitable for nitrification and denitrification. Submersed turbine aerators in oxidation ditch . including shock loads. Photo 11. pollution load. the main advantage of the OD is its resilience to variations in flow. Schematic diagram of oxidation ditches with BOD removal.

.0 kg/m2 per hour are generally used for secondary sedimentation of tannery effluents. very often nitrification and denitrification stages need to be introduced into the biological system. m/h). less than for primary clarifiers. In order to satisfy the legal limits for nitrogen (ammonia and TKN). these salts are converted under anoxic conditions into neutral nitrogen gas (N2) and water.e. Nitrification requires extensive aeration as well as a low F : M ratio (< 0. The overflow from the secondary clarifiers represents the fully treated effluent usually fit for discharge into a final recipient. Also. which for operational reasons can take place either at the very beginning or at the end of the biological treatment. i.5 m3/m2 per hour is generally used for secondary sedimentation of tannery effluents.0 and 3. SSR values between 2.1) to facilitate conversion of nitrogen containing organic matter into nitrate and nitrite salts. SOR of approximately 0. Oxidation ditch in operation 2. Surface solid rate (SSR) is the quantity per hour of MLSS (kg) crossing the surface area of the secondary sedimentation tank (kg/m2 of tank surface per hour) (see primary sedimentation). Surface hydraulic loading – or surface overflow rate (SOR) – is the vertical velocity of the influent in the secondary sedimentation tank (m3/m2 of tank surface per hour.. During the denitrification stage.6 Secondary sedimentators Their design is very similar to those of primary sedimentators. but the operational conditions are different. the (excess – wastage) sludge evacuated at the tank bottom is normally bulkier and more difficult to dewater.36 Secondary treatment Photo 12.

usually more sophisticated and rather expensive treatments such as mineralization of organic compounds by oxidation with H2O2 in the presence of ferrous sulphate (Fenton process and its derivatives). 3. i. despite its high performance. difficulties and risks in dealing with this gas prevail over other. The usual culprit is the recalcitrant COD.1 Mechanical sludge dewatering The main purpose of sludge dewatering is not only to reduce the volume and weight of material to be transported but also to attain the dry matter content required for disposal at landfills. (3) About 10 m3/h of clean water at 4 bars per meter of belt width are required for continuous belt washing. hydrogen sulphide (H2S). the quality of the final effluent does not meet the promulgated discharge limits. despite extensive physical-chemical and biological treatment in a well designed ETP. Advanced (tertiary) treatment In certain cases. but recommendable for enhancing filtration rate and general performance. compounds that the micro-organisms present in the floc are unable to decompose. (4) Periodical cleaning of filtering cloth is required (at least once per week). Here is a short comparative overview of the main characteristics and efficiencies of the various systems as well as changes in DS content throughout the treatment process. Ozonation is sometimes included not so much to kill potentially harmful micro-organisms but to destroy part of the residual COD. The equipment used for this purpose – recessed-plate filters. comparatively lower costs and wide use in other industries.Introduction to treatment of tannery effluents 37 2. Table 5. (2) Sludge conditioning with inorganic chemicals (iron salts and lime) is not strictly necessary. 4.e..7 Anaerobic biological treatment As mentioned earlier. Characteristics of sludge dewatering equipment (1) Polyelectrolyte (usually cationic): 2-4 g/kg of DS. belt presses and decanter centrifuges – was already described earlier. anaerobic treatment has failed to make inroads in the tanning industry. positive features of anaerobic treatment. corrosive and flammable gas. In such cases. it is necessary to resort to additional. The main reason is that tannery effluent treatment leads to the development of a highly toxic. . Sludge handling 4.

a detailed assessment of options should be prepared and the most suitable application proposed. A number of solutions for utilization and/or safe disposal of tannery sludge have been proposed. the main stumbling block is the chromium content. practiced. land application. none of them proving satisfactory enough. handling. storage and transport of sludge and solid wastes from PTPs and ETPs should also be safe and not contaminate the surroundings. Dry matter content in sludge depending on process stage and/or type of dewatering equipment 4. especially chromium and greater sulfur compound content. However. with legislation and practice varying a lot from country to country. Each ETP produces sludge of specific characteristics and different regions and countries have quite different regulations regarding sludge utilization. and applied at pilot and industrial scale: landfill. Therefore. for example). thermal treatment. brick making. thus.38 Sludge handling * Average values for mixed (primary + secondary) tannery sludges Table 6. Containers for solid waste .2 Utilization and disposal In comparison with sanitary sludges. etc. the collection points should be protected against bad weather (rain. vitrification. anaerobic digestion.. In any case. There is certainly no universal solution for sludge utilization/application. tannery sludge has greater inorganic matter content. Photo 13. composting. greater heavy metal content. for example. pyrolisys. tested. prior to any ETP construction.

Thus. (temporary) sludge disposal site. etc. More extensive. in-plant storage of dewatered sludge. biological aeration. amines. Along the treatment line. it is not the concentration of sulphide per se.Introduction to treatment of tannery effluents 39 5. it is crucial to control pH and. play an important role. Yet. Local geographic and climatic conditions such as wind direction. if needed. air humidity. the main source of bad smell remains the stripping of hydrogen sulphide. sludge thickening.). but sometimes rigorous (and expensive) methods such as adding hydrogen peroxide or pure oxygen are necessary. uninterrupted aeration may help. . nearly the entire ETP is covered and the air is purified. in some places. Nowadays. ground and air temperature.5-10. The issue of bad odour Odours associated with wastewater are difficult to quantify because they are caused by a wide variety of compounds and they are a nuisance that is more qualitative than quantitative – sensitive persons easily detect very low concentrations of odoriferous substances in the air (sulphides/other sulphur compounds. alkalis like NaOH or lime are added to achieve pH > 9. but the lowering of pH: the not disassociated H2S is present only at pH below 10. the main sources of bad smell are: • • • • • equalization and sulphide oxidation. land shape. etc. ammonia.

40 Secondary treatment Figure 33. Simplified flowchart of the biological (secondary) tannery effluent treatment .

Introduction to treatment of tannery effluents Figure 34. Simplified flowchart of a full-fledged tannery effluent treatment plant 41 .

while sludge handling and disposal costs are comparatively low. labour. etc. Figure 36. sludge volume index (SVI). OSH. management The extent of monitoring activities largely depends on local legal requirements and ETP size and it includes a wide range of parameters: effluent volume(s). chemical dosing. etc. chemicals. Distribution of average total costs at selected CETPs in Italy . peak loads. In industrialized countries. Figure 35. OSH. sludge utilization and disposal options. the largest component is power.42 Monitoring. The costs of treatment vary a lot. depending on the local costs of: • • • • • power. Monitoring. management 6. Structure of average treatment costs at selected CETPs in India in 2005 In developing countries. the cost of energy escalates further. costs. the largest cost component is dewatering and safe disposal of solids (sludge). pollution loads. dissolved oxygen (DO). costs. If the reverse osmosis (RO) stage for desalination is installed. financing.

for example.Introduction to treatment of tannery effluents 43 While working out the costs of an ETP at an individual tannery is quite straightforward. being based solely on effluent volume and type of tanning. Figure 37. Schematic chart of typical effluent treatment setup for clusters in developing countries Figure 38. sulphides and Cr. m3/day. • production capacity. In developing countries. whereas in Italy. crust or finished leather. different methods are applied to compute the distribution of CETP operation costs among individual tanneries. cost calculation methods for CETPs are usually very simple. suspended solids. these methods are very sophisticated and are based on many factors measured on-/off-line or estimated. Schematic chart of typical effluent treatment setup in industrialized countries . m2/day of wet blue. • production output. The key parameters used are typically the following: • water consumption. tonnes of wet-salted hides/day. • actual pollution load in terms of COD.

This explains the numerous accidents despite its known toxicity. . Otherwise.44 Monitoring. general and specific measures concerning equipment and chemicals also apply to ETPs. paradoxically. it is perceived only at lower concentrations. Poisoning effects of hydrogen sulphide gas (H2S) New toxicological data have led authorities in some countries to start reducing the recommended chronicexposure limits to hydrogen sulphide – the 8-hour time-weighted average of the threshold limit value (TLVTWA8) for H2S came down from 10 ppm to 1 ppm. Instruments used to detect and monitor H2S exposure can be either fixed or portable. this is a legal requirement. and the short-term exposure limit (TLV-STEL) from 15 ppm to 5 ppm. whereas personal detectors are worn by employees and typically sound an alarm at levels between 10 ppm and 15 ppm. Nowadays it is taken for granted that in a well managed tannery there is a person of appropriate competence and at an appropriate level of seniority who deals exclusively with increasingly complex environmental issues. even confirming compliance with the new standards will be a challenge. H2S meters are always positioned at critical points and/or carried by staff. costs. As mentioned earlier. hydrogen sulphide is an extremely toxic and irritating gas. the main focus is on hydrogen sulphide gas. in some countries. Due to this nearly permanent life threatening hazard. It has a strong odour of rotten eggs but. as a result. especially those related to effluent treatment. certain activities such as entering pits can be carried out only in the presence of skilled supervisors (the worker performing such an operation must also wear a safety harness). ppm = parts per million Table 7. OSH. management When it comes to occupational safety and health at work (OSH) in (C)ETPs. Also.

Introduction to treatment of tannery effluents 45 Figure 39. An example of CETP management setup .

46 Conclusions 7. and modular common effluent treatment plants servicing traditional tannery clusters or newly created leather industry zones is a widely accepted approach. Relocation of tanneries to the seaside is often not feasible. unaffected by treatment. This problem is especially pronounced in developing countries where mixing tannery effluent with domestic sewage or its discharge into the sea is not feasible. and the raw hides and skins are still preserved by salting. Cost-effective solutions to both of these problems are still eagerly awaited. Conclusions The treatment of tannery effluents is by now a well established technology. . However. and desalination of treated effluent by reverse osmosis is very expensive. two issues still pose serious challenges: • High TDS (salinity) content. • Utilization or safe disposal of sludge.

Annexes .

General view of inputs and outputs in the leather sector Annex 2.48 Annexes Annex 1. Chrome-recovery unit using NaOH .

Introduction to treatment of tannery effluents 49 Annex 3. Classification of pumps .

50 Annexes Annex 4. A model of rotary screening drum Annex 5. Types of sedimentation tanks .

Sludge production in leather processing . Photos and cross section of a circular sedimentation tank Annex 7.Introduction to treatment of tannery effluents 51 Annex 6.

52 Annexes Annex 8. Classification of mechanical aerators .

Scheme of the membrane bioreactor (MBR) Annex 10. . Personal hydrogen-gas monitor Note: This is one of many brands in the market.Introduction to treatment of tannery effluents 53 Annex 9.

Reverse osmosis (RO): principle.54 Annexes Annex 11. diagram. photo of a small RO unit .

Schematic view of constructed wetland – reed beds .Introduction to treatment of tannery effluents 55 Annex 12.

56 Annexes Annex 13. Aerated static composting pile .

Introduction to treatment of tannery effluents

57

Annex 14. Typical fluxogram of an ETP

It can be approximated that: The volume of raw effluent = influent to biological treatment = volume of treated effluent.

58 Annexes

Annex 15. A dialogue between a tanner and an environmental engineer
Information to be provided by the tanner: • Production: daily input and types of raw material (hides, skins; fresh/wet-salted), processing stage (wet blue, crust, finished), working days (per week/year, any closure periods), number of employees. • Process – present, plans for the future: biocides used, hair-save unhairing, deliming on low dose of ammonium salts, any degreasing, chrome management (direct recycling, high exhaustion, recovery). • Effluent emissions: – industrial (beamhouse, tanyard, general), segregation, total/peak/average flow, discharge distribution over the day; – rainwater – separate drainage, not mixed with industrial effluent; – sanitary effluents – separate drainage, not mixed with industrial effluent. • Raw effluent quality – detailed laboratory analysis of each of the three industrial streams and/or combined effluent: BOD5, COD, SS, Cr, TKN, NH3-N, chlorides, sulphates (TDS). • • • • • Nature of the recipient of treated effluent: sewage, open water body (river, lake). Officially (locally) prescribed quality of treated effluent – discharge limits. Area available for the ETP. Distance to residential areas. Any local solution for utilization and/or disposal of (chrome-containing) sludge.

Information about the local climate (temperatures, precipitations, wind directions), unit cost of electricity and chemicals, primarily polyelectrolytes, as well as labour costs should also be required if necessary. Questions a tanner should ask: In addition to obvious questions concerning investment and operation costs, the tanner should specifically focus the discussion on: • A detailed explanation regarding the logic of the overall technical concept. • A comparative evaluation of technical alternatives, e.g., bottom diffusers vs. Venturi ejectors for aeration, conventional tank vs. oxidation ditch for biology, frame-filter press vs. decanter centrifuge, etc. • The rate of purification for each treatment stage. • Emergency procedures – back-up arrangements in case of the failure of parts or larger components of the treatment system (e.g., collapse of the biological treatment). • Occupational safety and health measures, including personal protection equipment (PPE). • A concise overview of on- and off-line monitoring and control parameters, including the expected value ranges at critical points (presence of H2S, COD, DO, settleability, DS content, etc.). • Performance guarantee – warranty concerning the quality of the treated effluent in conformity with local legislation (discharge limits). • “If scenarios“ – provisions/buffers/safety margins/retrofitting/upgrades in case of failure to meet (additional) norms.

Introduction to treatment of tannery effluents

59

Annex 16. Basic plant monitoring and control
Local legal requirements are crucial in determining the extent and frequency of tests conducted to monitor and control ETP performance to satisfy discharge limits. Obviously, for that purpose, full laboratory tests in accordance with (international) standardized procedures are required. However, regular monitoring of key parameters is also important for optimizing the treatment process and reducing operation costs. It is also assumed that recording of some parameters like effluent volumes is automated and that H2S meters are always positioned at critical points and/or carried by staff in accordance with Occupational Safety and Health (OSH) norms and procedures.

Italy and India 1As phenolic compounds (as C H OH). no discharge limits pertaining to chlorides. Note: The data in the table above refer to the year 2002. chlorides: 1. sulphates: 1.100 mg/l.500 mg/l. for discharge in surface water and sewer. (The authorities do not insist on norms relating to COD and nitrogen.60 Annexes Annex 17.at Solofra – chlorides: 3. ** In Tamil Nadu. .at Arzignano – chlorides: 900 mg/l. This relates exclusively to effluent discharged in a sewer). 6 5 * Special limits permitted by the regional authorities to certain CETPs located close to the sea or if the effluent is mixed with sanitary wastewater: . Previously. sulphates: 1. India – TDS limit: 2. . .500 mg/l TDS were tolerated by the authorities.500 mg/l.at Santa Croce.000 mg/l.000 mg/l.000 mg/l.800 mg/l. Discharge limits for treated tannery effluents in France. sulphates and TDS have been prescribed except in special cases. up to 7. CuoioDepur and Fuccechino – chlorides: 5. *** In France.800 mg/l. sulphates: 1. if the effluent is treated alongside with domestic sewage in a combined treatment plant. sulphates: 1.

Introduction to treatment of tannery effluents 61 Annex 18. Typical tannery ETP auxiliary chemicals and their dosing* * Always in solution. .

As a result. if they emerge from the factory. The problems can be very serious when blockages occur in inaccessible piping. Depending on effluent composition. They can be easily removed by means of coarse bar screens set in the wastewater flow. the main problems that arise are due to the large volume of sludge that forms as the solids settle. Semi-colloidal solids will not directly cause a sludge problem. Sludge often contains up to 97% water. dewatered. 2. giving rise to huge quantities of “light” sludge. transported. All this sludge has to be removed. The waste components that give rise to this problem are often large pieces of leather cuttings. equipment and resources. These insoluble materials cause a variety of problems when discharged. If effluent with a high oxygen demand is discharged directly into surface water. they settle out very rapidly. Their presence. Even viscous sludge has a water content of about 93% and can easily block sumps.62 Annexes Annex 19. sludge pumps and pipes. They can be broken down over an extended period by bacterial digestion and produce solids. Semi-colloidal solids Semi-colloidal solids are very fine solids that. b. is clear to see and the dangers they pose are fully recognized. the debris rapidly accumulates causing blockages and leading to stagnation. thus placing an inordinate strain on plant. Environmental effects of the main constituents of tannery effluents Solids 1. will not settle out even if the effluent is left to stand for a considerable period of time. this breakdown can be quite rapid or may take a very long time. aquatic life dies and decomposition sets in. however. Gross solids Gross solids are larger than those a sampling machine can handle. The cost of replacing burned-out motors or broken rotors is high. there are two types of solids distinguished by significantly different characteristics. Major problems can develop if these materials settle in the pipes since they lead to blockages. Even a thin layer of settled sludge can become a blanket that deprives sections of the river or lake bed of oxygen. However. essentially. Oxygen demand Many effluent components are broken down by bacterial action into simpler components. dried and deposited. fleshing residues. the sensitive balance . hence they are not measured. trimmings and gross shavings. ditches or water courses. a. which will eventually settle. If discharged into gullies. Suspended solids Suspended solids present in effluents are defined as the quantity of insoluble matter contained in the wastewater. Solids with a rapid settling rate (settleable solids) If wastewaters are to be treated in sewage works or to undergo traditional effluent treatment. solid hair debris and remnants of paper bags. for all practical purposes. Oxygen is required for both the survival of these (aerobic) bacteria and the breakdown of the components.

vegetable tanning wastes have a long breakdown period. and the effluent requires treatment prior to discharge. Some chemicals will only be partially broken down. Chemical oxygen demand (COD) This method measures the oxygen required to oxidize the effluent sample entirely. a disproportionately high amount of organic matter has to be broken down. Biochemical oxygen demand (BOD5) The BOD5 analysis. The load created by tanneries. A healthy river can tolerate substances with low levels of oxygen demand. the longer-term biodegradable products. including certain re-tanning agents. dyes. Typically. These longer digestion periods can apply to a variety of chemicals used in manufacturing leather. If the load outstrips the natural supply of oxygen from the river. Sometimes.5 mg/l. and residual proteins from hair solubilization. as well as the chemicals that remain unaffected by bacterial activity. is often excessive. As the plants die. Total Kjeldahl nitrogen (TKN) Several tannery effluent components contain nitrogen as part of their chemical structure. The semi-colloidal material in suspended solids is also included in the BOD and COD determinations. while others may not be significantly affected. It should also be noted that. oxygen demand needs to be determined. . Oxygen is stripped from the water causing oxygendependent plants. but the high levels released by substances containing nitrogen over-stimulate growth. This can be done in two different ways: 1. 2. many effluent components take longer than the period of analysis to break down. In order to assess the impact of effluent discharge on surface waters or determine the cost of treatment. fish – as well as the river or stream itself – to die. The outcome is an environment populated by anaerobic bacteria (which are not oxygen-dependent) leading to toxic water conditions. plants. whereupon waterways become clogged and their flow is impaired. however. generally called BOD. these sources have to be differentiated. The most common chemicals are ammonia (from deliming materials) and the nitrogen contained in proteinaceous materials (from liming/unhairing operations). Nitrogen Nitrogen is contained in several tannery effluent components. Normally 1 mg/l of suspended solids will generate a COD increase of approximately 1. while BOD is a measure of the oxygen requirements of bacteria under controlled conditions. It sets a value for the materials that would normally be digested in the BOD5 analysis. These sources of nitrogen pose two direct problems: a. is widely used to assess the environmental demands of wastewater.Introduction to treatment of tannery effluents 63 maintained in the water becomes overloaded. fish and aerobic bacteria die and ultimately anaerobic conditions develop. bacteria. Plants require nitrogen in order to grow. Water-based plants and algae grow too rapidly. some synthetic fat liquors. This longer breakdown period means that the environmental impact is spread over a larger area as wastewater components are carried over greater distances before breaking down. often quoted as being up to 20 days.

In sewers. if excessive. girders and building supports. however. the higher the rate of evolution.5. Many auxiliary chemicals contain sodium sulphate as a by-product of their manufacture. major problems can arise as metal fittings. In its toxicity. even low concentrations pose toxic hazards. hydrogen sulphide is comparable to hydrogen cyanide. weak acids can form and cause corrosion. Both of these breakdown products are non-toxic. At higher levels. since the oxidation process produces a whole range of substances. When absorbed. as do many synthetic re-tanning agents. thus leading to correspondingly high operational and energy costs. Sulphates (SO4)2Sulphates are a component of tannery effluent which emanates from the use of sulphuric acid or products with a high (sodium) sulphate content. Sulphides can be oxidized into non-toxic compounds by certain bacteria in rivers. For example. this creates oxygen demand that. Neutral salts Two common types of salts are to be found in tannery effluent: 1. death can rapidly set in. which is ultimately released into the atmosphere. When the pH of the effluent drops below 9. hydrogen sulphide evolves from the effluent: the lower the pH. Calculations show that. sulphides remain largely in solution. even a low level of exposure to the gas induces headaches and nausea. including sodium sulphate. and countless deaths attributable to the build-up of sulphide in sewage systems have been recorded. Sulphides (S2-) The sulphide content in tannery effluent results from the use of sodium sulphide and sodium hydrosulphide and the breakdown of hair in the unhairing process. yet large amounts of oxygen are needed in the process. Under alkaline conditions. Bacteria can convert the latter over several stages into water and nitrogen gas. If discharged into surface water.64 Annexes b. some 40% of oxygen requirements are spent on removing the nitrogen component. This weakens metal roofing. chrome tanning powders contain high levels of sodium sulphate. The oxygen demand is very high. with typical tannery effluent. Removing the sulphide component from effluent by aeration creates an additional source. If oxygen demand is greater than the level supplied naturally by the body of water. a severe odour problem occurs. Characterized by a smell of rotten eggs. Sulphates can be . Sulphides pose many problems. The nitrogen released through protein breakdown and the deliming process is in the form of ammonia. Hydrogen sulphide gas is also soluble. structural reinforcements and piping corrode. as well as possible eye damage. can harm aquatic life. toxic anaerobic conditions can rapidly develop. Combining intensive aerobic and anoxic biological treatment can break down the nitrogenous compounds.

2. greater tolerance is shown towards higher pH values since carbon dioxide from the atmosphere or from biological processes in healthy surface water systems tends to lower pH levels very effectively to neutral conditions. they create a very high oxygen demand on account of their bio-degradability. surface salinity increases through evaporation and crop yields fall. Generally. . If these fatty substances emulgate. some fatty substances may be produced through inter-reaction when wastewaters mingle.” which then bind other materials. oxygen transfer from the atmosphere is reduced. is now becoming a serious environmental hazard. If fat liquor exhaustion is poor. If the water is used for irrigation purposes.5. Problems arise with soluble sulphates. sewage systems and water courses. if effluents remain static. thus causing a potential blockage problem especially in effluent treatment systems. When flushed from the soil by rain. This process occurs very rapidly in effluent treatment plants. Considerable quantities of salt are produced by industry and levels can rapidly rise to the maximum level acceptable for drinking water. Under certain biological conditions. natural oils and grease are released from within the skin structure. If the surface water pH shifts too far either way from the pH range of 6. for two main reasons: a.0. Increased salt content in groundwater.5 to pH 10. concrete will gradually erode. chlorides re-enter the eco-system and may ultimately end up in the groundwater. If no breakdown occurs. it is possible to remove sulphate from a solution and bind the sulphur into micro-organisms. Being highly soluble and stable. Sulphates cannot be removed completely from a solution by chemical means.5-7. sensitive fish and plant life may be lost. If the surface waters are contaminated with grease or thin layers of oil. Oils and grease In leather manufacture. This bacterial conversion to hydrogen sulphide in sewage systems results in the corrosion of metal parts. Chlorides (Cl-) Chloride is introduced into tannery effluents as sodium chloride usually on account of the large quantities of common salt used in hide and skin preservation or the pickling process. high levels can lead to breakdowns in cell structure. bacteria and fish in surface waters. however. pH value Acceptable limits for the discharge of wastewaters into both surface waters and sewers vary. and unless it is sulphate-resistant. b. thus remaining as a burden on the environment. especially in areas of high industrial density. Although stricter limits are often set. there is the risk of increasing the total concentration of salts in surface waters and groundwater. the sulphate either remains as sulphate or is broken down by anaerobic bacteria to produce malodorous hydrogen sulphide.Introduction to treatment of tannery effluents 65 precipitated by calcium-containing compounds to form calcium sulphate that has a low level of solubility. Chlorides inhibit the growth of plants. it is not affected by effluent treatment and nature. Floating grease and fatty particles agglomerate to form “mats. however. ranging from pH 5.

chrome VI) Dichromates are toxic to fish life since they swiftly penetrate cell walls. Two forms of chrome are associated with the tanning industry. the pH is lowered to more neutral conditions by carbon dioxide. This chrome is discharged in soluble form. Even in low concentrations. Once successfully broken down.66 Annexes Municipal and common treatment plants prefer discharges to be more alkaline to reduce the corrosive effect on concrete. and hydrogen sulphide evolution is minimized. however. it occurs as part of the re-tanning system and is displaced from leathers during re-tanning and dyeing processes. the chromium might remain in the solution. and the biological process in both surface waters and treatment plants is inhibited. tannery effluents are unlikely to contain chromium in this form. Chromium compounds Metal compounds are not biodegradable. thus disrupting the food chain for fish life and possibly inhibiting photosynthesis. the reaction is very rapid. chrome III) Chromium is mainly found in waste from the chrome tanning process. the protein has been partially tanned. Chrome 3+ (trivalent chrome. 2. Very fine colloids are also formed which are then stabilized by the chrome – in effect. When biological processes are included in the treatment. Precipitates are formed. mainly protein-chrome. . they are the subject of close attention. Chrome 6+ (hexavalent chrome. 1. and their properties are often confused. They are mainly absorbed through the gills and the effect is accumulative. Metals tend to remain insoluble and more inert. They can thus be regarded as long-term environmental features. it has a toxic effect upon daphnia. when mixed with tannery wastewaters from other processes (especially if proteins are present). The components are thus highly resistant to biological breakdown. Since they can also have accumulative properties. chromium hydroxide precipitates and persists in the ecosystem for an extended period of time. which add to sludge generation. However. If chrome discharges are excessive.

Future Trends in the Leather and Leather Products Industry and Trade 67 Annex 20. M. Mexico. Aloy. T. Bibliothek des Leders. J.waterspecialists. UNIDO Leather Industry Panel meeting. M. 3. Swaminathan. Manual on landfill for tannery sludge. Gramado. Rio Grande do Sul.jp/ietc/publications/freshwater/sb_summary/10. Chinese). J. LGR.fao. Ökologische Probleme der Lederindustrie. Pollutants in tannery effluents: Definitions and environmental impact. 10. Some considerations about the problem of salinity of tannery effluents. Bosnic. Ludvik. Sahasranaman & CTC. J. Lieselotte Feikes. Poncet. Buljan. G.asp . 2.biz/html/about_coagulation_flocculati. French. 1990. Occupational safety and health aspects of leather manufacture (OSH manual).org/docrep/t0551e/t0551e05. UNIDO Leather Industry Panel meeting. 11. 12. Hannak. March 2004. J. 4. Buljan. Daniels. References 1. Aloy. Hannak.or. M. Buljan. Spanish. 1991.unep. http://www. Jayaraj. V. limits for discharge into water bodies and sewers. J. Brazil. R. 2.P. IULTCS Congress. Mass balance in leather processing. http://www. 1997. UNEP-UNIDO. 7. Auflage. Post. Band 8. Costs of tannery waste treatment. May 2007.htm 13. Buljan. 6. A. 8. J. G. Tanneries and the environment: A technical guide. (English. Selection of equipment for laboratories monitoring pollution in the tanning industry. J. Buljan. 9. J. 5.html http://www. Safety handbook: How to deal with hydrogen sulphide gas in tanneries and effluent treatment plants. Germany. September 2005. León. Reich. Benchmarking in the tanning industry. J. R. Buljan.

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